3&#39;-nitro-4&#39;-acidylamido-o-benzoyl-benzoic acids and process of making the same



1 dium, hydrogen or the like:

Patented July 16, 1929.

. noean ADAMS m wannnm. wnmmu MOYER, or

URBANA, ILLINOIS, assmnons TO THE NEWPORT COMPANY, OF CABROLLVILLE, WISCONSIN, A CORPORATIQN or DELAWARE.

3-NITRO-4-ACIDYLAMIDO-O-BENZOYL-IBENZOIC ACIDS AND PROCESS OF MAKING THE No Drawing.

This invention relates to 3-nitro-4'-acidylamido-o-benzoyl-benzoic acids and to a process of making the same.

It is an ob ect of this invention to provide 5. a method of preparing 3'-n'itro4-aci'dylamido-o-benzoyl-benzoic acids, which are val. uable compounds in the preparation of dyestufi intermediates.

Other and further important objects of this invention will become apparent from the disclosures in the following description and appended claims.

In the Adams et al. Patent, No. 1,614,584, it is pointed out that derivativesof benzoyl o-benzoicacid containing a nitro and an amino group inortho position may be prepared by the condensation of ammonia, or primary or secondary amines with 3-nitro- 4-chloro-benzoyl-o-benzoic acid.

The present invention contemplates the preparation of substituted amido compounds by the condensation of acidyl substituted ammonia compounds with 3"-nitro-4-chloro-0 benzoyl-benzoic acid, according to the fol-' lowing equations, wherein R represents an aryl nucleus such as phenyl, tolyl and the like and R represents an aryl nucleus such as phenyl, naphthyl and the like, and wherein M represents a metallic element such as so- I NOr- N as g o.+ R-SOr-NH, r o "H01 A 00011 I O-eoon 40 7 n o0 o1 N/ n' oo 9 3.

Y o0 V 3 o ,R -n-. o 1101 l I OOH 00H These bodies are in general crystalline soli'ds, which may be easily recrystallized from Application filed July 9, 1927. Serial No. 204,655.

. v glacial acetic acid. .The melting point of 3-nitro-4'-benzene-sulphonamido-o-benzoylbenzoic acid is a'bout213 C., that of 3-nitro- 4'-(p-toluene-su1phonamido) -0-benzoyl-benzoic acid is about 229 C. with decomposition. Without limiting our 'invention to any particular procedure, the following example, in which parts by weight are given, illustrates the application of our invention in the preferred form:

Example I .3'-nitro -4- (p toluene sulphonamido)-o-benzoyl-benzoic acid. A mixture-M305 parts of 4-chloro-3 nitro-o-benzoyl-benzoic acid, 18.8 parts of p-toluene-sulphonamide, 30 parts of anhydrous potassium carbonate, 1.5 parts of copper acetate and 0.8 parts ofcopper powder are added to 200 parts of nitro benzene. The

composite mixture is then heated in an oil bath to 180190 C., under an air cooled refiux' condenser with occasional shaking. The reaction apparently-starts in at about (1' and continues with increased speed up to C. Within one hour the reactionv 1s essentially completed as evidenced by the cessation of boiling and the settlingto the bottom of. the flask of an orange colored solid.

'The nitro-benzene is now steam distilled from the reaction mass, after which the residual solution is filtered. The product is is0- lated by acidifying the filtrate with dilute hydrochloric acid, whereb it is recipitated from the solution in the ormoi cream colored crystals. The crystals are filtered ofi, washed with cold water, and dried. They may be recrystallized from glacial acetic acid.

The purified product has a melting (point un-- der decomposition of about 229 and is robably best represented by thefollowmg ormula: c

. n-N-sorO-am con E I la II.-3'-nitro-4=- benzene sulphon' ainido-o-benzoyl-benzoic acid.

amide. The product has the following formula We are aware that numerous details of the process may be varied through a wide range Without departing from the principles of this invention, and We therefore, do not purpose limiting the patent granted hereon, otherwise than necessitated by tlieprior art.

We claim-as our invention:

1. The process of preparing a 3ni'tro-4'- acidylamido-o-benzoyl-benzoic acid, which comprises condensing 3-nitro-4- -hloro-obenzoyl-benzoic acid with an acid'yl substituted ammonia.

2. The process of preparing a 3'-nitro-4'- acidylamido-o-benzoyl-benzoic acid, which comprises condensing 3'-nitro-4-chloro-obenzoyl-benzoic acid in nitro-benzene with an 'acidyl substituted ammonia in the presence of a copper catalyst.

3. Jlhe process of preparing compounds of the general formula:

- Q-o o- N-SOz-R benzoyl-bgnzoic acid in a suitable solvent with the corresponding substituted ammonia.

4. The process of preparing 3-nitro-4- (p-toluene-sulphonamido) -o-benzoyl-benzoic acid, which comprises condensing 3-nitro-4- (p-toluene-su1phona1nido) -o-benzoyl-benzoic acid in nitro benzene with p'tolucne-sulphonamide-in the presence of a copper catalyst.

5. As new articles of manufacture, 3- nitrO-l'-acidylamido-o-benzoyl-benzoic acids.

,6. As new articles of manufacture, compounds of the general formula P1 O0 o-Gr'r-sm-m c 'oou wherein R represents an aryl nucleus.

7. As a new article of manufacture, 3'- nitro 4 (p-toluene sulphonamido) -o-benzoyl-b'enzoic acid.

In testimony whereof we have hereunto subscribed our names at Urbana, Champaign County, Illinois. I

ROGER ADAMS. WENDELL WILLIAM MOYER. 

